Stabilizer mixtures

ABSTRACT

A stabilizer mixture containing
     (I) two different sterically hindered amine compounds, and   (II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide.

This is a continuation of application Ser. No. 10/945,514, filed on Sep. 20, 2004, which is a continuation of Ser. No. 09/899,438, filed on Jul. 5, 2001, now granted U.S. Pat. No. 6,828,364 on Dec. 7, 2004.

The present invention relates to a stabilizer mixture containing two different sterically hindered amine compounds and at least one Mg- and/or Zn-compound, the use of this mixture for stabilizing an organic material, in particular a polyolefin, against degradation induced by light, heat or oxidation and the organic material thus stabilized.

The stabilization of polyolefins is described in numerous publications, for example in U.S. Pat. No. 4,929,652, U.S. Pat. No. 5,025,051, U.S. Pat. No. 5,037,870, EP-A-276,923, EP-A-290,388, EP-A-429,731, EP-A-468,923, EP-A-661,341, EP-A-690,094, DE-A-19,545,896 (Derwent 96-278,994/29; Chemical Abstracts 125:116779q), WO-A-95/25,767, GB-A-2,293,827, Chemical Abstracts 106:197407z, GB-A-2,332,678, WO-A-00/11,065, GB-A-2,316,409, GB-A-2, 332,677, Chemical Abstracts 132: 335,575t and Research Disclosure 34,549.

In more detail, the present invention relates to

a stabilizer mixture containing (I) two different sterically hindered amine compounds, and (II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide; with the proviso that component (I) is different from the combination of the compounds (B-8-a) and (B-8-b)

wherein n₂ and n₂* are a number from 2 to 50; and with the proviso that, when component (I) is the combination of the compounds (B-1-a-1) and (B-7-a);

wherein b₁ is a number from 2 to 50,

wherein n₁ is a number from 2 to 50; and, at the same time, component (II) is a Zn carboxylate; the stabilizer mixture additionally contains as a further component (X-1) a pigment or (X-2) an UV absorber or (X-3) a pigment and an UV absorber.

A preferred embodiment of the present invention relates to a stabilizer mixture containing as component (I) two different sterically hindered amine compounds wherein one sterically hindered amine compound is a compound of the formula (B-1-b) or (B-1-d)

wherein b₁ is a number from 2 to 20 and R₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl; and the other sterically hindered amine compound is a compound of the formula (B-7-a)

wherein n₁ is a number from 2 to 20; and component (II) is an organic salt of Zn, an inorganic salt of Zn, Zn oxide or Zn hydroxide; preferably Zn carboxylate.

Preferably, a stabilizer mixture containing a compound of the class (β-1) as defined below, a compound of the class (β-7) as defined below and Zn-carboxylate, in particular an organic salt of Zn, is disclaimed.

According to a preferred embodiment of the present invention, component (II) is an organic salt of Mg, an inorganic salt of Mg, Mg oxide or Mg hydroxide, when component (I) is the combination of a compound of the class (β-1) as defined below, and a compound of the class (β-7) as defined below.

The stabilizer mixtures according to the present invention preferably do not contain a mineral oil.

The two different sterically hindered amine compounds of component (I) are preferably selected from the group consisting of the following classes

(α-1) a compound of the formula (A-1)

in which E₁ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl, m₁ is 1, 2 or 4, if m₁ is 1, E₂ is C₁-C₂₅alkyl, if m₁ is 2, E₂ is C₁-C₁₄alkylene or a group of the formula (a-I)

wherein E₃ is C₁-C₁₀alkyl or C₂-C₁₀alkenyl, E₄ is C₁-C₁₀alkylene, and E₅ and E₆ independently of one another are C₁-C₄alkyl, cyclohexyl or methylcyclohexyl, and if m₁ is 4, E₂ is C₄-C₁₀alkanetetrayl; (α-2) a compound of the formula (A-2)

in which two of the radicals E₇ are —COO—(C₁-C₂₀alkyl), and two of the radicals E₇ are a group of the formula (a-II)

with E₈ having one of the meanings of E₁; (α-3) a compound of the formula (A-3)

in which E₉ and E₁₀ together form C₂-C₁₄alkylene, E₁₁ is hydrogen or a group -Z₁-COO-Z₂, Z₁ is C₂-C₁₄alkylene, and Z₂ is C₁-C₂₄alkyl, and E₁₂ has one of the meanings of E₁; (α-4) a compound of the formula (A-4)

wherein the radicals E₁₃ independently of one another have one of the meanings of E₁, the radicals E₁₄ independently of one another are hydrogen or C₁-C₁₂alkyl, and E₁₅ is C₁-C₁₀alkylene or C₃-C₁₀alkylidene; (α-5) a compound of the formula (A-5)

wherein the radicals E₁₆ independently of one another have one of the meanings of E₁; (α-6) a compound of the formula (A-6)

in which E₁₇ is C₁-C₂₄alkyl, and E₁₈ has one of the meanings of E₁; (α-7) a compound of the formula (A-7)

in which E₁₉, E₂₀ and E₂₁ independently of one another are a group of the formula (a-III)

wherein E₂₂ has one of the meanings of E₁; (α-8) a compound of the formula (A-8)

wherein the radicals E₂₃ independently of one another have one of the meanings of E₁, and E₂₄ is hydrogen, C₁-C₁₂alkyl or C₁-C₁₂alkoxy; (α-9) a compound of the formula (A-9)

wherein m₂ is 1, 2 or 3, E₂₅ has one of the meanings of E₁, and when m₂ is 1, E₂₆ is a group

when m₂ is 2, E₂₆ is C₂-C₂₂alkylene, and when m₂ is 3, E₂₆ is a group of the formula (a-IV)

wherein the radicals E₂₇ independently of one another are C₂-C₁₂alkylene, and the radicals E₂₈ independently of one another are C₁-C₁₂alkyl or C₅-C₁₂cycloalkyl; (α-10) a compound of the formula (A-10)

wherein the radicals E₂₉ independently of one another have one of the meanings of E₁, and E₃₀ is C₂-C₂₂alkylene, C₅-C₇cycloalkylene, C₁-C₄alkylenedi(C₅-C₇cycloalkylene), phenylene or phenylenedi(C₁-C₄alkylene); (β-1) a compound of the formula (B-1)

in which R₁, R₃, R₄ and R₅ independently of one another are hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, phenyl which is substituted by —OH and/or C₁-C₁₀alkyl; C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I)

R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene or C₁-C₄alkylenedi(B₅—C₇cycloalkylene), or the radicals R₁, R₂ and R₃, together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or R₄ and R₅, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, R₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉-phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl, and b₁ is a number from 2 to 50, with the proviso that at least one of the radicals R₁, R₃, R₄ and R₅ is a group of the formula (b-I); (β-2) a compound of the formula (B-2)

wherein — R₇ and R₁₁ independently of one another are hydrogen or C₁-C₁₂alkyl, R₈, R₉ and R₁₀ independently of one another are C₂-C₁₀alkylene, and X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are a group of the formula (b-II),

in which R₁₂ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, —OH— and/or C₁-C₁₀alkyl-substituted phenyl, C₇-C₉-phenylalkyl, C₇-C₉-phenylalkyl which is substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I) as defined above, and R₁₃ has one of the meanings of R₆; (β-3) a compound of the formula (B-3)

in which R₁₄ is C₁-C₁₀alkyl, C₅-C₁₂cycloalkyl, C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl or C₁-C₁₀alkyl-substituted phenyl, R₁₅ is C₃-C₁₀alkylene, R₁₆ has one of the meanings of R₆, and b₂ is a number from 2 to 50; (β-4) a compound of the formula (B-4)

in which R₁₇ and R₂₁ independently of one another are a direct bond or a —N(X₉)—CO—X₁₀—CO—N(X₁₁)—group, where X₉ and X₁₁ independently of one another are hydrogen, C₁-C₈alkyl, C₅-C₁₂cycloalkyl, phenyl, C₇-C₉phenylalkyl or a group of the formula (b-I), X₁₀ is a direct bond or C₁-C₄alkylene, R₁₈ has one of the meanings of R₆, R₁₉, R₂₀, R₂₃ and R₂₄ independently of one another are hydrogen, C₁-C₃₀alkyl, C₅-C₁₂cycloalkyl or phenyl, R₂₂ is hydrogen, C₁-C₃₀alkyl, C₅-C₁₂cycloalkyl, phenyl, C₇-C₉phenylalkyl or a group of the formula (b-I), and b₃ is a number from 1 to 50; (β-5) a compound of the formula (B-5)

in which R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ independently of one another are a direct bond or C₁-C₁₀alkylene, R₃₀ has one of the meanings of R₆, and b₄ is a number from 1 to 50; (β-6) a product (B-6) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1) with cyanuric chloride, with a compound of the formula (B-6-2)

in which b′₅, b″₅ and b′″₅ independently of one another are a number from 2 to 12, R₃₁ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl, and R₃₂ has one of the meanings of R₆; (β-7) a compound of the formula (B-7)

wherein A₁ is hydrogen or C₁-C₄alkyl, A₂ is a direct bond or C₁-C₁₀alkylene, and n₁ is a number from 2 to 50; (β-8) at least one compound of the formulae (B-8-a) and (B-8-b)

wherein n₂ and n₂* are a number from 2 to 50; (β-9) a compound of the formula (B-9)

wherein A₃ and A₄ independently of one another are hydrogen or C₁-C₈alkyl, or A₃ and A₄ together form a C₂-C₁₄alkylene group, and the variables n₃ independently of one another are a number from 1 to 50; and (β-10) a compound of the formula (B-10)

wherein n₄ is a number from 2 to 50, A₅ is hydrogen or C₁-C₄alkyl, the radicals A₆ and A₇ independently of one another are C₁-C₄alkyl or a group of the formula (b-I), with the proviso that at least 50% of the radicals A₇ are a group of the formula (b-I).

Examples of component (I) are:

-   -   A compound selected from the class α-1 and a compound selected         from the class α-3, α-5, α-6, α-7, α-9, α-10, β-1, β-2, β-3,         β-4, β-5, β-6, β-7, β-8 or β-9.     -   A compound selected from the class α-3 and a compound selected         from the class α-5, α-6, α-7, α-9, α-10, β-1, β-2, β-3, β-4,         β-5, β-6, β-7, β-8 or β-9.     -   A compound selected from the class α-5 and a compound selected         from the class α-6, α-7, α-9, α-10, β-1, β-2, β-3, β-4, β-5,         β-6, β-7, β-8 or β-9.     -   A compound selected from the class α-6 and a compound selected         from the class α-9, α-10, β-1, β-2, β-3, β-4, β-5, β-6, β-7, β-8         or β-9.     -   A compound selected from the class α-7 and a compound selected         from the class α-9, α-10, β-1, β-2, β-3, β-4, β-5, β-6, β-7, β-8         or β-9.     -   A compound selected from the class α-10 and a compound selected         from the class β-1, β-2, β-3, β-4, β-5, β-6, β-7, β-8 or β-9.     -   A compound selected from the class β-1 and a compound selected         from the class β-2, β-3, β-4, β-5, β-6, β-7, β-8 or β-9 or β-10.     -   A compound selected from the class β-2 and a compound selected         from the class β-3, β-4, β-5, β-6, β-7, β-8, β-9 or β-10.     -   A compound selected from the class β-3 and a compound selected         from the class β-4, β-5, β-6, β-7, β-8, β-9 or β-10.     -   A compound selected from the class β-4 and a compound selected         from the class β-5, β-6, β-7, β-8, β-9 or β-10.     -   A compound selected from the class β-5 and a compound selected         from the class β-6, β-7, β-8, β-9 or β-10.     -   A compound selected from the class β-6 and a compound selected         from the class β-7, β-8, β-9 or β-10.     -   A compound selected from the class β-7 and a compound selected         from the class β-8, β-9 or β-10.     -   A compound selected from the class β-8 and a compound selected         from the class β-9 or β-10.     -   A compound selected from the class β-9 and a compound selected         from the class β-10.

According to a preferred embodiment,

the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the classes (α-1), (α-2), (α-3), (α-4), (α-5), (α-6), (α-7), (α-8), (α-9) and (α-10).

According to a further preferred embodiment,

the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the classes (β-1), (β-2), (β-3), (β-4), (β-5), (β-6), (β-7), (β-8), (β-9) and (β-10).

According to another preferred embodiment,

one of the two different sterically hindered amine compounds of component (I) is selected from the group consisting of the classes (α-1), (α-2), (α-3), (α-4), (α-5), (α-6), (α-7), (α-8), (α-9) and (α-10), and the other of the two different sterically hindered amine compounds of component (I) is selected from the group consisting of the classes (β-1), (β-2), (β-3), (β-4), (β-5), (β-6), (β-7), (β-8), (β-9) and (β-10).

One of the two different sterically hindered amine compounds of component (I) is preferably selected from the class (β-1).

According to a particularly preferred embodiment,

one of the two different sterically hindered amine compounds of component (I) is selected from the class (β-1), and the other of the two different sterically hindered amine compounds of component (I) is selected from the class (α-1) or (β-7).

According to another particularly preferred embodiment,

one of the two different sterically hindered amine compounds of component (I) is selected from the class (β-7), and the other of the two different sterically hindered amine compounds of component (I) is selected from the class (β-2).

The two different sterically hindered amine compounds of component (I) are preferably selected from different classes.

Examples of alkyl having up to 30 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl and triacontyl. One of the preferred definitions of E₁, E₈, E₁₂, E₁₃, E₁₆, E₁₈, E₂₂, E₂₃, E₂₅, E₂₉, R₆, R₁₃, R₁₆, R₁₈, R₃₀ and R₃₂ is C₁-C₄alkyl, especially methyl. R₃₁ is preferably butyl.

Examples of alkoxy having up to 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. One of the preferred meanings of E₁ is octoxy. E₂₄ is preferably C₁-C₄alkoxy and one of the preferred meanings of R₆ is propoxy.

Examples of C₅-C₁₂cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. C₅-C₈Cycloalkyl, especially cyclohexyl, is preferred.

C₁-C₄Alkyl-substituted C₅-C₁₂cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.

Examples of C₅-C₁₂cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C₅-C₈Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.

—OH— and/or C₁-C₁₀alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl.

Examples of C₇-C₉phenylalkyl are benzyl and phenylethyl.

C₇-C₉Phenylalkyl which is substituted on the phenyl radical by —OH and/or by alkyl having up to 10 carbon atoms is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.

Examples of alkenyl having up to 10 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.

Examples of acyl containing not more than 8 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyl and benzoyl. C₁-C₈Alkanoyl, C₃-C₈alkenyl and benzoyl are preferred. Acetyl and acryloyl are especially preferred.

Examples of alkylene having up to 22 carbon atoms are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.

An example of C₃-C₁₀alkylidene is the group

An example of C₄-C₁₀alkanetetrayl is 1,2,3,4-butanetetrayl.

An example of C₅-C₇cycloalkylene is cyclohexylene.

An example of C₁-C₄alkylenedi(C₅-C₇cycloalkylene) is methylenedicyclohexylene.

An example of phenylenedi(C₁-C₄alkylene) is methylene-phenylene-methylene or ethylene-phenylene-ethylene.

Where the radicals R₁, R₂ and R₃, together with the nitrogen atoms to which they are attached, form a 5- to 10-membered heterocyclic ring, this ring is for example

A 6-membered heterocyclic ring is preferred.

Where the radicals R₄ and R₅, together with the nitrogen atom to which they are attached, form a 5- to 10-membered heterocyclic ring, this ring is for example 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl or 4,5,5,7-tetramethyl-1-homopiperazinyl. Morpholino is particularly preferred.

One of the preferred definitions of R₁₉ and R₂₃ is phenyl.

R₂₆ is preferably a direct bond.

n₁, n₂, n₂* and n₄ are preferably a number from 2 to 25, in particular 2 to 20. n₃ is preferably a number from 1 to 25, in particular 1 to 20.

b₁ and b₂ are preferably a number from 2 to 25, in particular 2 to 20.

b₃ and b₄ are preferably a number from 1 to 25, in particular 1 to 20.

b′₅ and b′″₅ are preferably 3 and b″₅ is preferably 2.

The compounds described above as components (I) and (II) are essentially known and commercially available. All of them can be prepared by known processes.

The preparation of the compounds of component (I) is disclosed, for example, in U.S. Pat. No. 5,679,733, U.S. Pat. No. 3,640,928, U.S. Pat. No. 4,198,334, U.S. Pat. No. 5,204,473, U.S. Pat. No. 4,619,958, U.S. Pat. No. 4,110,306, U.S. Pat. No. 4,110,334, U.S. Pat. No. 4,689,416, U.S. Pat. No. 4,408,051, SU-A-768,175 (Derwent 88-138,751/20), U.S. Pat. No. 5,049,604, U.S. Pat. No. 4,769,457, U.S. Pat. No. 4,356,307, U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,182,390, GB-A-2,269,819, U.S. Pat. No. 4,292,240, U.S. Pat. No. 5,026,849, U.S. Pat. No. 5,071,981, U.S. Pat. No. 4,547,538, U.S. Pat. No. 4,976,889, U.S. Pat. No. 4,086,204, U.S. Pat. No. 6,046,304, U.S. Pat. No. 4,331,586, U.S. Pat. No. 4,108,829, U.S. Pat. No. 5,051,458, WO-A-94/12,544 (Derwent 94-177,274/22), DD-A-262,439 (Derwent 89-122,983/17), U.S. Pat. No. 4,857,595, U.S. Pat. No. 4,529,760, U.S. Pat. No. 4,477,615, CAS 136,504-96-6, U.S. Pat. No. 4,233,412, U.S. Pat. No. 4,340,534, WO-A-98/51,690 and EP-A-1,803.

The product (B-6) can be prepared analogously to known processes, for example by reacting a polyamine of formula (B-6-1) with cyanuric chloride in a molar ratio of from 1:2 to 1:4 in the presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol at a temperature of from −20° C. to +10° C., preferably from −10° C. to +10° C., in particular from 0° C. to +10° C., for from 2 to 8 hours, followed by reaction of the resultant product with a 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2). The molar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of the formula (B-6-1) employed is for example from 4:1 to 8:1. The quantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be added in one portion or in more than one portion at intervals of a few hours.

The molar ratio of polyamine of the formula (B-6-1) to cyanuric chloride to 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-6-2) is preferably from 1:3:5 to 1:3:6.

The following example indicates one way of preparing a preferred product (B-6-a).

EXAMPLE

23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol) of N,N′-bis[3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of anhydrous potassium carbonate are reacted at 5° C. for 3 hours with stirring in 250 ml of 1,2-dichloroethane. The mixture is warmed at room temperature for a further 4 hours. 27.2 g (0.128 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine are added and the resultant mixture is warmed at 60° C. for 2 hours. A further 18 g (0.13 mol) of anhydrous potassium carbonate are added and the mixture is warmed at 60° C. for a further 6 hours. The solvent is removed by distillation under a slight vacuum (200 mbar) and replaced by xylene. 18.2 g (0.085 mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine and 5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixture is heated at reflux for 2 hours and, for a further 12 hours, the water formed during the reaction is removed by azeotropic distillation. The mixture is filtered. The solution is washed with water and dried over Na₂SO₄. The solvent is evaporated and the residue is dried at 120-130° C. in vacuo (0.1 mbar). The desired product is obtained as a colourless resin.

In general, the product (B-6) can, for example, be represented by a compound of the formula (B-6-α), (B-6-β) or (B-6-γ). It can also be in the form of a mixture of these three compounds.

A preferred meaning of the formula (B-6-α) is

A preferred meaning of the formula (B-6-β) is

A preferred meaning of the formula (B-6-γ) is

In the above formulae (B-6-α) to (B-6-γ), b₅ is preferably 2 to 20, in particular 2 to 10.

The two different sterically hindered amine compounds of component (I) are preferably selected from the group consisting of the following commercial products:

DASTIB 845®, TINUVIN 770®, TINUVIN 765®, TINUVIN 144®, TINUVIN 123®, MARK LA 52®, MARK LA 57®, MARK LA 62®, MARK LA 67®, HOSTAVIN N 20®, HOSTAVIN N 24®, SANDUVOR 3050®, DIACETAM 5®, SUMISORB TM 61®, UVINUL 4049®, SANDUVOR PR 31®, GOODRITE UV 3034®, GOODRITE UV 3150®, GOODRITE UV 3159®, GOODRITE 3110 x 128®, UVINUL 4050H®, CHIMASSORB 944®, CHIMASSORB 2020®, CYASORB UV 3346®, CYASORB UV 3529®, DASTIB 1082®, CHIMASSORB 119®, UVASIL 299®, UVASIL 125®, UVASIL 2000®, UVINUL 5050H®, LICHTSCHUTZSTOFF UV 31®, LUCHEM HA B 18®, MARK LA 63®, MARK LA 68®, UVASORB HA 88®, TINUVIN 622®, HOSTAVIN N 30® and FERRO AM 806®.

The meanings of the terminal groups which saturate the free valences in the compounds of the formulae (B-1), (B-3), (B-4), (B-5), (B-6-α), (B-6-β), (B-6-γ), (B-7), (B-8-α), (B-8-b) and (B-10) depend on the processes used for their preparation. The terminal groups can also be modified after the preparation of the compounds.

If the compounds of the formula (B-1) are prepared by reacting a compound of the formula

in which X is, for example, halogen, in particular chlorine, and R₄ and R₅ are as defined above, with a compound of the formula

in which R₁, R₂ and R₃ are as defined above, the terminal group bonded to the diamino radical is hydrogen or

and the terminal group bonded to the triazine radical is X or

If X is halogen, it is advantageous to replace this, for example, by —OH or an amino group when the reaction is complete. Examples of amino groups which may be mentioned are pyrrolidin-1-yl, morpholino, —NH₂, —N(C₁-C₈)alkyl)₂ and —NR(C₁-C₈alkyl), in which R is hydrogen or a group of the formula (b-I).

The compounds of the formula (B-1) also cover compounds of the formula

wherein R₁, R₂, R₃, R₄, R₅ and b₁ are as defined above and R₄* has one of the meanings of R₄ and R₅* has one of the meanings of R₅.

One of the particularly preferred compounds of the formula (B-1) is

The preparation of this compound is described in Example 10 of U.S. Pat. No. 6,046,304.

In the compounds of the formula (B-3), the terminal group bonded to the silicon atom can be, for example, (R₁₄)₃Si—O—, and the terminal group bonded to the oxygen can be, for example, —Si(R₁₄)₃.

The compounds of the formula (B-3) can also be in the form of cyclic compounds if b₂ is a number from 3 to 10, i.e. the free valences shown in the structural formula then form a direct bond.

In the compounds of the formula (B-4), the terminal group bonded to the 2,5-dioxopyrrolidine ring is, for example, hydrogen, and the terminal group bonded to the —C(R₂₃)(R₂₄)— radical is, for example,

In the compounds of the formula (B-5), the terminal group bonded to the carbonyl radical is, for example,

and the terminal group bonded to the oxygen radical is, for example,

In the compounds of the formulae (B-6-α), (B-6-β) and (B-6-γ), the terminal group bonded to the triazine radical is, for example, Cl or a

group, and the terminal group bonded to the amino radical is, for example, hydrogen or a

group.

If the compounds of the formula (B-7) are prepared, for example, by reacting a compound of the formula

in which A₁ is hydrogen or methyl, with a dicarboxylic acid diester of the formula Y—OOC-A₂-COO—Y, in which Y is, for example, methyl, ethyl or propyl, and A₂ is as defined above, the terminal group bonded to the 2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or —CO-A₂COO—Y, and the terminal group bonded to the diacyl radical is —O—Y or

In the compounds of the formula (B-8-a), the terminal group bonded to the nitrogen can be, for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene radical can be, for example, a

group.

In the compounds of the formula (B-8-b), the terminal group bonded to the dimethylene radical can be, for example, —OH, and the terminal group bonded to the oxygen can be, for example, hydrogen. The terminal groups can also be polyether radicals.

In the compounds of the formula (B-10), the end group bonded to the —CH₂— residue can be, for example, hydrogen and the end group bonded to the —CH(CO₂A₇) residue can be, for example, —CH═CH—COOA₇.

E₁, E₈, E₁₂, E₁₃, E₁₆, E₁₈, E₂₂, E₂₃, E₂₅, E₂₉, R₆, R₁₃, R₁₆, R₁₈, R₃₀ and R₃₂ are preferably hydrogen, C₁-C₄alkyl, C₁-C₁₀alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.

E₁, E₈, E₁₂, E₁₃, E₁₆, E₁₈, E₂₂, E₂₃, E₂₅, E₂₉, R₆, R₁₃, R₁₆, R₁₈, R₃₀ and R₃₂ are in particular hydrogen or methyl and E₁ and R₆ additionally are C₁-C₈alkoxy.

According to a preferred embodiment,

m₁ is 1, 2 or 4, if m₁ is 1, E₂ is C₁₂-C₂₀alkyl, if m₁ is 2, E₂ is C₂-C₁₀alkylene or a group of the formula (a-I) E₃ is C₁-C₄alkyl, E₄ is C₁-C₆alkylene, and E₅ and E₆ independently of one another are C₁-C₄alkyl, and if m₁ is 4, E₂ is C₄-C₈alkanetetrayl; two of the radicals E₇ are —COO—(C₁₀-C₁₅alkyl), and two of the radicals E₇ are a group of the formula (a-II); E₉ and E₁₀ together form C₉-C₁₃alkylene, E₁₁ is hydrogen or a group -Z₁-COO-Z₂, Z₁ is C₂-C₆alkylene, and Z₂ is C₁₀-C₁₆alkyl; E₁₄ is hydrogen, and E₁₅ is C₂-C₆alkylene or C₃-C₅alkylidene; E₁₇ is C₁₀-C₁₄alkyl; E₂₄ is C₁-C₄alkoxy; m₂ is 1, 2 or 3, when m₂ is 1, E₂₆ is a group

when m₂ is 2, E₂₆ is C₂-C₆alkylene, and when m₂ is 3, E₂₆ is a group of the formula (a-IV) the radicals E₂₇ independently of one another are C₂-C₆alkylene, and the radicals E₂₈ independently of one another are C₁-C₄alkyl or C₅-C₈cycloalkyl; and E₃₀ is C₂-C₈alkylene; R₁ and R₃ independently of one another are a group of the formula (b-I), R₂ is C₂-C₈alkylene, R₄ and R₅ independently of one another are hydrogen, C₁-C₁₂alkyl, C₅-C₈cycloalkyl or a group of the formula (b-I), or the radicals R₄ and R₅, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and b₁ is a number from 2 to 25; R₇ and R₁₁ independently of one another are hydrogen or C₁-C₄alkyl, R₈, R₉ and R₁₀ independently of one another are C₂-C₄alkylene, and X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are a group of the formula (b-II), R₁₂ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl or a group of the formula (b-I); R₁₄ is C₁-C₄alkyl, R₁₅ is C₃-C₆alkylene, and b₂ is a number from 2 to 25; R₁₇ and R₂₁ independently of one another are a direct bond or a group —N(X₉)—CO—X₁₀—CO—N(X₁₁)—, X₉ and X₁₁ independently of one another are hydrogen or C₁-C₄alkyl, X₁₀ is a direct bond, R₁₉ and R₂₃ are C₁-C₂₅alkyl or phenyl, R₂₀ and R₂₄ are hydrogen or C₁-C₄alkyl, R₂₂ is C₁-C₂₅alkyl or a group of the formula (b-I), and b₃ is a number from 1 to 25; R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ independently of one another are a direct bond or C₁-C₄alkylene, and b₄ is a number from 1 to 25; b′₅, b″₅ and b′″₅ independently of one another are a number from 2 to 4, and R₃₁ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl, phenyl or benzyl; A₁ is hydrogen or methyl, A₂ is a direct bond or C₂-C₆alkylene, and n₁ is a number from 2 to 25; n₂ and n₂* are a number from 2 to 25; A₃ and A₄ independently of one another are hydrogen or C₁-C₄alkyl, or A₃ and A₄ together form a C₉-C₁₃alkylene group, and the variables n₃ independently of one another are a number from 1 to 25; n₄ is a number from 2 to 25, A₅ and A₆ independently of one another are C₁-C₄alkyl, and A₇ is C₁-C₄alkyl or a group of the formula (b-I) with the proviso that at least 50% of the radicals A₇ are a group of the formula (b-I).

The two different sterically hindered amine compounds of component (I) are preferably selected from the group consisting of the compounds of the formulae (A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a), (A-3-b), (A-4-a), (A-4-b), (A-5), (A-6-a), (A-7), (A-8-a), (A-9-a), (A-9-b), (A-9-c), (A-10-a), (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-4-a), (B-4-b) and (B-4-c), a product (B-6-a) and the compounds of the formulae (B-7-a), (B-8-a), (B-8-b), (B-9-a) and (B-10-a);

wherein E₁ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl;

in which two of the radicals E₇ are —COO—C₁₃H₂₇ and two of the radicals E₇ are

and E₈ has one of the meanings of E₁;

wherein E₁₂ has one of the meanings of E₁;

wherein E₁₃ has one of the meanings of E₁;

wherein E₁₆ has one of the meanings of E₁;

wherein E₁₈ has one of the meanings of E₁;

in which E₁₉, E₂₀ and E₂₁ independently of one another are a group of the formula (a-III)

wherein E₂₂ has one of the meanings of E₁;

wherein E₂₃ has one of the meanings of E₁;

wherein E₂₅ has one of the meanings of E₁;

wherein E₂₉ has one of the meanings of E₁;

wherein b₁ is a number from 2 to 20 and R₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl;

wherein R₁₃ has one of the meanings of R₆,

wherein b₂ is a number from 2 to 20 and R₁₆ has one of the meanings of R₆;

wherein b₃ is a number from 1 to 20 and R₁₈ has one of the meanings of R₆;

wherein b₄ is a number from 1 to 20 and R₃₀ has one of the meanings of R₆; a product (B-6-a) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1-a) with cyanuric chloride, with a compound of the formula (B-6-2-a)

in which R₃₂ has one of the meanings of R₆;

wherein n₁ is a number from 2 to 20;

wherein n₂ and n₂* are a number from 2 to 20;

wherein the variables n₃ independently of one another are a number from 1 to 20;

wherein n₄ is a number from 2 to 20, and at least 50% of the radicals A₇ are a group of the formula (b-I)

wherein R₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl, and the remaining radicals A₇ are ethyl.

According to a preferred embodiment,

the two different sterically hindered amine compounds of component (I) are

-   1) a compound of the formula (A-1-b) wherein E₁ is hydrogen, and a     compound of the formula (B-1-a) wherein R₆ is hydrogen; -   2) a compound of the formula (B-1-a) wherein R₆ is hydrogen, and a     compound of the formula (B-7-a); or -   3) a compound of the formula (B-2-a) wherein R₁₃ is methyl, and a     compound of the formula (B-7-a).

The organic salt of zinc or magnesium defined in component (II) is preferably a compound of the formula MeL₂ in which Me is zinc or magnesium and L is an anion of an organic acid or of an enol. The organic acid can, for example, be a sulfonic acid, sulfinic acid, phosphonic acid or phosphinic acid, but is preferably a carboxylic acid. The acid can be aliphatic, aromatic, araliphatic or cycloaliphatic; it can be linear or branched; it can be substituted by hydroxyl or alkoxy groups; it can be saturated or unsaturated and it preferably contains 1 to 24 carbon atoms.

Examples of carboxylic acids of this type are formic, acetic, propionic, butyric, isobutyric, caprioic, 2-ethylcaproic, caprylic, capric, lauric, palmitic, stearic, behenic, oleic, lactic, ricinoleic, 2-ethoxypropionic, benzoic, salicylic, 4-butylbenzoic, toluic, 4-dodecylbenzoic, phenylacetic, naphthylacetic, cyclohexanecarboxylic, 4-butylcyclohexanecarboxylic or cyclohexylacetic acid. The carboxylic acid can also be a technical mixture of carboxylic acids, for example technical mixtures of fatty acids or mixtures of alkylated benzoic acids.

Examples of organic acids containing sulfur or phosphorus are methanesulfonic, ethanesulfonic, α,α-dimethylethanesulfonic, n-butanesulfonic, n-dodecanesulfonic, benzenesulfonic, toluenesulfonic, 4-nonylbenzenesulfonic, 4-dodecylbenzenesulfonic or cyclohexanesulfonic acid, dodecanesulfinic, benzenesulfinic or naphthalenesulfinic acid, butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethyl phenylphosphonate, monobutyl benzylphosphonate, dibutylphosphinic acid or diphenylphosphinic acid.

If L is an enolate anion, it is preferably an anion of a β-dicarbonyl compound or of an o-acylphenol. Examples of β-dicarbonyl compounds are acetylacetone, benzoylacetone, dibenzoylmethane, ethyl acetoacetate, butyl acetoacetate, lauryl acetoacetate or α-acetylcyclohexanone. Examples of o-acylphenols are 2-acetylphenol, 2-butyroylphenol, 2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The enolate is preferably the anion of a β-dicarbonyl compound having 5 to 20 carbon atoms.

Organic salts of zinc or magnesium are preferably an acetylacetonate or an aliphatic monocarboxylate having, for example, 1 to 24 carbon atoms. Magnesium acetate, laurate and stearate, zinc formate, acetate, oenanthate, laurate and stearate as well as zinc acetylacetonate and magnesium acetylacetonate are some of the particular preferred examples.

Zinc stearate, magnesium stearate, zinc acetylacetonate, magnesium acetylacetonate, zinc acetate and magnesium acetate are of special interest.

The inorganic salt of zinc or magnesium is for example

a carbonate containing compound such as

-   -   Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite, e.g a         Ca/Mg carbonate such as Microdol Super® from Micro Minerals®; or     -   a natural or synthetic hydrotalcite.

The natural hydrotalcite is held to possess a structure Mg₆Al₂(OH)₁₆CO₃.4 H₂O.

A typical empirical formula of a synthetic hydrotalcite is

Al₂Mg_(4.35)OH_(11.36)CO_(3(1.67)).x H₂O.

Examples of the synthetic product include:

Mg_(0.7)Al_(0.3)(OH)₂(CO₃)_(0.15).0.54 H₂O, Mg_(4.5)Al₂(OH)₁₃CO₃.3.5 H₂O, or Mg_(4.2)Al(OH)_(12.4)CO₃.

Preferred synthetic hydrotalcites are L-55R II® from REHEIS® as well as ZHT-4A® and DHT4A® from Kyowa Chemical Industry Co®.

Component (II) can also be a mixture of two different Mg- and/or Zn-compounds, for example

-   -   Mg-stearate and hydrotalcite (DHT-4A®),     -   Zn-stearate and hydrotalcite (DHT-4A®),     -   Mg-acetylacetonate and hydrotalcite (DHT-4A®),     -   Mg-oxide and hydrotalcite (DHT-4A®),     -   Mg-hydroxide and hydrotalcite (DHT-4A®),     -   Zn-hydroxide-carbonate and Mg-stearate,     -   Zn-hydroxide-carbonate and Zn-stearate,     -   Zn-hydroxide-carbonate and Mg-acetylacetonate,     -   Zn-hydroxide-carbonate and Mg-oxide,     -   Zn-hydroxide-carbonate and Zn-oxide,     -   Zn-hydroxide-carbonate and Mg-hydroxide,     -   hydrotalcite (REHEIS®) and Mg-stearate,     -   hydrotalcite (REHEIS®) and Zn-stearate,     -   hydrotalcite (REHEIS®) and Mg-oxide,     -   dolomite (Microdol Super®) and Zn-stearate,     -   dolomite (Microdol Super®) and Mg-stearate,     -   dolomite (Microdol Super®) and Zn-oxide,     -   dolomite (Microdol Super®) and Mg-hydroxide,     -   Mg-stearate and Zn-stearate,     -   Mg-stearate and Zn-acetylacetonate,     -   Mg-stearate and Mg-oxide,     -   Mg-stearate and Zn-oxide,     -   Mg-stearate and Mg-hydroxide,     -   Zn-stearate and Mg-acetate,     -   Zn-stearate and Mg-oxide,     -   Zn-stearate and Mg-hydroxide,     -   Mg-acetylacetonate and Zn-acetylacetonate,     -   Mg-acetylacetonate and Mg-oxide,     -   Mg-acetylacetonate and Zn-oxide,     -   Mg-acetylacetonate and Mg-hydroxide,     -   Zn-acetylacetonate and Mg-oxide,     -   Zn-acetylacetonate and Zn-oxide, or     -   Mg-oxide and Zn-oxide.

In this case, the two different compounds of component (II) may be present in a weight ratio of 1:10 to 10:1.

A preferred embodiment of this invention relates to a stabilizer mixture wherein the compound(s) of component (II) is (are) selected from the group consisting of Mg carboxylates, Zn carboxylates, Mg oxides, Zn oxides, Mg hydroxides, Zn hydroxides, Mg carbonates and Zn carbonates.

Another preferred embodiment of this invention relates to a stabilizer mixture wherein component (II) is a Mg carboxylate, a Zn carboxylate, a hydrotalcite, or a mixture of a Mg carboxylate and a hydrotalcite.

A particularly preferred embodiment of this invention relates to a stabilizer mixture wherein component (II) is Mg stearate, Zn stearate, a hydrotalcite, in particular DHT-4A®, or a mixture of Mg stearate and a hydrotalcite.

Preferred examples of stabilizer mixtures according to the present invention are:

1. TINUVIN 622®+CHIMASSORB 944®+Mg stearate 2. TINUVIN 622®+CHIMASSORB 119®+Mg stearate 3. TINUVIN 622®+CHIMASSORB 2020®+Mg stearate 4. TINUVIN 622®+CYASORB UV 3346®+Mg stearate 5. TINUVIN 622®+CYASORB UV 3529®+Mg stearate 6. TINUVIN 622®+UVASORB HA 88®+Mg stearate 7. TINUVIN 622®+UVINUL 5050H®+Mg stearate 8. TINUVIN 622®+ADK STAB LA 63®+Mg stearate 9. TINUVIN 622®+ADK STAB LA 68®+Mg stearate 10. TINUVIN 622®+UVASIL 299 HM®+Mg stearate 11. TINUVIN 622®+TINUVIN 770®+Mg stearate 12. TINUVIN 622®+TINUVIN 765®+Mg stearate 13. TINUVIN 622®+TINUVIN 123®+Mg stearate 14. TINUVIN 622®+HOSTAVIN N 20®+Mg stearate 15. TINUVIN 622®+ADK STAB LA 52®+Mg stearate 16. TINUVIN 622®+ADK STAB LA 57®+Mg stearate 17. TINUVIN 622®+CYASORB UV 3581®+Mg stearate 18. TINUVIN 622®+CYASORB UV 3641®+Mg stearate 19. TINUVIN 622®+UVINUL 4050H™+Mg stearate 20. TINUVIN 622®+DASTIB 845®+Mg stearate 21. TINUVIN 770®+CHIMASSORB 944®+Mg stearate 22. TINUVIN 770®+CHIMASSORB 119®+Mg stearate 23. TINUVIN 770®+CHIMASSORB 2020®+Mg stearate 24. TINUVIN 770®+CYASORB UV 3346®+Mg stearate 25. TINUVIN 770®+CYASORB UV 3529®+Mg stearate 26. TINUVIN 770®+UVASORB HA 88®+Mg stearate 27. TINUVIN 770®+UVINUL 5050H®+Mg stearate 28. TINUVIN 770®+ADK STAB LA 63®+Mg stearate 29. TINUVIN 770®+ADK STAB LA 68®+Mg stearate 30. TINUVIN 770®+UVASIL 299 HM®+Mg stearate 31. TINUVIN 770®+TINUVIN 765®+Mg stearate 32. TINUVIN 770®+TINUVIN 123®+Mg stearate 33. TINUVIN 770®+HOSTAVIN N 20®+Mg stearate 34. TINUVIN 770®+ADK STAB LA 52®+Mg stearate 35. TINUVIN 770®+ADK STAB LA 57®+Mg stearate 36. TINUVIN 770®+CYASORB UV 3581®+Mg stearate 37. TINUVIN 770®+CYASORB UV 3641®+Mg stearate 38. TINUVIN 770®+UVINUL 4050H™+Mg stearate 39. TINUVIN 770®+DASTIB 845®+Mg stearate 40. CHIMASSORB 944®+CHIMASSORB 119®+Mg stearate 41. CHIMASSORB 944®+CHIMASSORB 2020®+Mg stearate 42. CHIMASSORB 944®+CYASORB UV 3346®+Mg stearate 43. CHIMASSORB 944®+CYASORB UV 3529®+Mg stearate 44. CHIMASSORB 944®+UVASORB HA 88®+Mg stearate 45. CHIMASSORB 944®+UVINUL 5050H®+Mg stearate 46. CHIMASSORB 944®+ADK STAB LA 63®+Mg stearate 47. CHIMASSORB 944®+ADK STAB LA 68®+Mg stearate 48. CHIMASSORB 944®+UVASIL 299 HM®+Mg stearate 49. CHIMASSORB 944®+TINUVIN 765®+Mg stearate 50. CHIMASSORB 944®+TINUVIN 123®+Mg stearate 51. CHIMASSORB 944®+HOSTAVIN N 20®+Mg stearate 52. CHIMASSORB 944®+ADK STAB LA 52®+Mg stearate 53. CHIMASSORB 944®+ADK STAB LA 57®+Mg stearate 54. CHIMASSORB 944®+CYASORB UV 3581®+Mg stearate 55. CHIMASSORB 944®+CYASORB UV 3641®+Mg stearate 56. CHIMASSORB 944®+UVINUL 4050H®+Mg stearate 57. CHIMASSORB 944®+DASTIB 845®+Mg stearate 58. CHIMASSORB 119®+CYASORB UV 3529®+Mg stearate 59. CHIMASSORB 119®+ADK STAB LA 63®+Mg stearate 60. CHIMASSORB 119®+TINUVIN 765®+Mg stearate 61. CHIMASSORB 119®+TINUVIN 123®+Mg stearate 62. CHIMASSORB 119®+ADK STAB LA 52®+Mg stearate 63. CHIMASSORB 119®+CYASORB UV 3641®+Mg stearate

The formulations obtained by replacing in the formulations 2 to 63 Mg stearate by Zn stearate are also preferred. Further, the formulations 1 to 66 wherein Mg stearate is replaced by DHT-4A or Mg oxide or by combinations of the coadditives listed as component (II) are preferred.

Examples of the latter formulations are:

1. TINUVIN 622®+CHIMASSORB 944®+DHT-4A®+Mg stearate 2. TINUVIN 770®+CHIMASSORB 944®+DHT4A®+Mg stearate 3. TINUVIN 622®+CHIMASSORB 119®+DHT-4A®+Mg stearate 4. TINUVIN 770®+UVASORB HA 88®+DHT-4A®+Mg stearate 5. TINUVIN 622®+UVASORB HA 88®+DHT-4A®+Mg stearate 6. TINUVIN 622®+UVASIL 299®+DHT-4A®+Mg stearate 7. TINUVIN 622®+CHIMASSORB 2020®+DHT-4A®+Mg stearate 8. TINUVIN 770®+CHIMASSORB 2020®+DHT-4A®+Mg stearate

The commercial product TINUVIN 622® corresponds to the compound of the formula (B-7-a).

The commercial product CHIMASSORB 944® corresponds to the compound of the formula (B-1-a) wherein R₆ is hydrogen.

The commercial product CHIMASSORB 119® corresponds to the compound of the formula (B-2-a) wherein R₁₃ is methyl.

The commercial product CHIMASSORB 2020® corresponds to the compound of the formula (B-1-b) wherein R₆ is hydrogen.

The commercial product CYASORB UV 3346® corresponds to the compound of the formula (B-1-d) wherein R₆ is hydrogen.

The commercial product CYASORB UV 3529® corresponds to the compound of the formula (B-1-d) wherein R₆ is methyl.

The commercial product UVASORB HA 88® corresponds to the product (B-6-a) wherein R₃₂ is hydrogen.

The commercial product UVINUL 5050H® corresponds to the compound of the formula (B-4-a) wherein R₁₈ is hydrogen.

The commercial product ADK STAB LA 63® corresponds to the compound of the formula (B-5-a) wherein R₃₀ is methyl.

The commercial product ADK STAB LA 68® corresponds to the compound of the formula (B-5-a) wherein R₃₀ is hydrogen.

The commercial product UVASIL 299® corresponds to the compound of the formula (B-3-a) wherein R₁₆ is hydrogen.

The commercial product TINUVIN 770® corresponds to the compound of the formula (A-1-b) wherein E₁ is hydrogen.

The commercial product TINUVIN 765® corresponds to the compound of the formula (A-1-b) wherein E₁ is methyl.

The commercial product TINUVIN 123® corresponds to the compound of the formula (A-1-b) wherein E₁ is octyloxy.

The commercial product HOSTAVIN N 20® corresponds to the compound of the formula (A-3-a) wherein E₁₂ is hydrogen.

The commercial product ADK STAB LA 52® corresponds to the compound of the formula (A-1-d) wherein E₁ is methyl.

The commercial product ADK STAB LA 57® corresponds to the compound of the formula (A-1-d) wherein E₁ is hydrogen.

The commercial product CYASORB UV 3581® corresponds to the compound of the formula (A-6-a) wherein E₁₈ is hydrogen.

The commercial product CYASORB UV 3641® corresponds to the compound of the formula (A-6-a) wherein E₁₈ is methyl.

The commercial product UVINUL 4050H® corresponds to the compound of the formula (A-10-a) wherein E₂₉ is hydrogen.

The commercial product DASTIB 845® corresponds to the compound of the formula (A-1-a) wherein E₁ is hydrogen.

A further preferred embodiment of this invention relates to a stabilizer mixture containing additionally

(X-1) a pigment or (X-2) an UV absorber or (X-3) a pigment and an UV absorber.

The pigment (component (X-1)) may be an inorganic or organic pigment.

Examples of inorganic pigments are titanium dioxide, zinc oxide, carbon black, cadmium sulfide, cadmium selenide, chromium oxide, iron oxide, lead oxide and so on.

Examples of organic pigments are azo pigments, anthraquinones, phthalocyanines, tetrachloroisoindolinones, quinacridones, isoindolines, perylenes, pyrrolopyrroles (such as Pigment Red 254) and so on.

All pigments described in “Gächter/Müller: Plastics Additives Handbook, 3rd Edition, Hanser Publishers, Munich Vienna New York”, page 647 to 659, point 11.2.1.1 to 11.2.4.2 can be used as component (X-1).

A particularly preferred pigment is titanium dioxide, optionally in combination with an organic pigment.

Examples of such organic pigments are:

C.I. (Colour Index) Pigment Yellow 93, C.I. Pigment Yellow 95, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 155, C.I. Pigment Yellow 162, C.I. Pigment Yellow 168, C.I. Pigment Yellow 180, C.I. Pigment Yellow 183, C.I. Pigment Red 44, C.I. Pigment Red 170, C.I. Pigment Red 202, C.I. Pigment Red 214, C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 272, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1, C.I. Pigment Green 7, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:3 and C.I. Pigment Violet 19.

Examples of the UV absorber (component (X-2)) are a 2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an ester of substituted or unsubstituted benzoic acid, an acrylate, an oxamide, a 2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or a formamidine.

The 2-(2′-hydroxyphenyl)benzotriazole is e.g. 2-(2′-hydroxy-5′-methylphenyl)-benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, mixture of 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol] or the transesterification product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R—CH₂CH₂—COO(CH₂)₃—]₂ where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

2-(3′,5′-Di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole and 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)-benzotriazole are preferred.

The 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy or 2′-hydroxy-4,4′-dimethoxy derivatives.

2-Hydroxy-4-octyloxybenzophenone is preferred.

The ester of a substituted or unsubstituted benzoic acid is for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate are preferred.

The acrylate is for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-di-phenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxy-cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycinnamate or N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

The oxamide is for example 4, 4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide or its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide or mixtures of ortho- and para-methoxy-disubstituted oxanilides or mixtures of o- and p-ethoxy-disubstituted oxanilides.

The 2-(2-hydroxyphenyl)-1,3,5-triazine is for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine or 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine are preferred.

The monobenzoate of resorcinol is for example the compound of the formula

The formamidine is for example the compound of the formula

The UV absorber is in particular a

2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone or a hydroxyphenyltriazine.

A further preferred embodiment of this invention relates to a stabilizer mixture which additionally contains as a further component (XX) an organic salt of Ca, an inorganic salt of Ca, Ca oxide or Ca hydroxide.

Examples of an organic salt of Ca are Ca-stearate, Ca-laurate, Ca-lactate and Ca-stearoyl-lactate.

Examples of an inorganic salt of Ca are CaCO₃, CaCl₂, CaF₂, Ca₃(PO₄)₂, CaHPO₄, Ca(PO₃)₂, Ca₂P₂O₇, CaSO₄ and CaSiO₃.

Further preferred examples of stabilizer mixtures according to the present invention are:

a. TINUVIN 622®+CHIMASSORB 944®+Mg stearate+Ca stearate b. TINUVIN 770®+CHIMASSORB 944®+Mg stearate+Ca stearate c. TINUVIN 622®+CHIMASSORB 119®+Mg stearate+Ca stearate d. TINUVIN 770®+UVASORB HA 88®+Mg stearate+Ca stearate e. TINUVIN 622®+UVASORB HA 88®+Mg stearate+Ca stearate f. TINUVIN 622®+UVASIL 299®+Mg stearate+Ca stearate g. TINUVIN 622®+CHIMASSORB 2020®+Mg stearate+Ca stearate h. TINUVIN 770®+CHIMASSORB 2020®+Mg stearate+Ca stearate i. TINUVIN 622®+CHIMASSORB 944®+DHT-4A®+Ca stearate j. TINUVIN 770®+CHIMASSORB 944®+DHT-4A®+Ca stearate k. TINUVIN 622®+CHIMASSORB 119®+DHT4A®+Ca stearate l. TINUVIN 770®+UVASORB HA 88®+DHT-4A®+Ca stearate m. TINUVIN 622®+UVASORB HA 88®+DHT-4A®+Ca stearate n. TINUVIN 622®+UVASIL 299®+DHT-4A®+Ca stearate o. TINUVIN 622®+CHIMASSORB 2020®+DHT-4A®+Ca stearate p. TINUVIN 770®+CHIMASSORB 2020®+DHT-4A®+Ca stearate

The stabilizer mixture according to this invention is suitable for stabilizing organic materials against degradation induced by light, heat or oxidation. Examples of such organic materials are the following:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE), or polyvinyl cyclohexane.

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at         elevated temperature).     -   b) catalytic polymerisation using a catalyst that normally         contains one or more than one metal of groups IVb, Vb, VIb or         VIII of the Periodic Table. These metals usually have one or         more than one ligand, typically oxides, halides, alcoholates,         esters, ethers, amines, alkyls, alkenyls and/or aryls that may         be either π or σ-coordinated. These metal complexes may be in         the free form or fixed on substrates, typically on activated         magnesium chloride, titanium(III) chloride, alumina or silicon         oxide. These catalysts may be soluble or insoluble in the         polymerisation medium. The catalysts can be used by themselves         in the polymerisation or further activators may be used,         typically metal alkyls, metal hydrides, metal alkyl halides,         metal alkyl oxides or metal alkyloxanes, said metals being         elements of groups Ia, IIa and/or III a of the Periodic Table.         The activators may be modified conveniently with further ester,         ether, amine or silyl ether groups. These catalyst systems are         usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),         TNZ (DuPont), metallocene or single site catalysts (SSC).         2. Mixtures of the polymers mentioned under 1), for example         mixtures of polypropylene with polyisobutylene, polypropylene         with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of         different types of polyethylene (for example LDPE/HDPE).         3. Copolymers of monoolefins and diolefins with each other or         with other vinyl monomers, for example ethylene/propylene         copolymers, linear low density polyethylene (LLDPE) and mixtures         thereof with low density polyethylene (LDPE),         propylene/but-1-ene copolymers, propylene/isobutylene         copolymers, ethylene/but-1-ene copolymers, ethylene/hexene         copolymers, ethylene/methylpentene copolymers, ethylene/heptene         copolymers, ethylene/octene copolymers, propylene/butadiene         copolymers, isobutylene/isoprene copolymers, ethyllene/alkyl         acrylate copolymers, ethylene/alkyl methacrylate copolymers,         ethylene/vinyl acetate copolymers and their copolymers with         carbon monoxide or ethylene/acrylic acid copolymers and their         salts (ionomers) as well as terpolymers of ethylene with         propylene and a diene such as hexadiene, dicyclopentadiene or         ethylidene-norbornene; and mixtures of such copolymers with one         another and with polymers mentioned in 1) above, for example         polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl         acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers         (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random         polyalkylene/carbon monoxide copolymers and mixtures thereof         with other polymers, for example polyamides.         4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated         modifications thereof (e.g. tackifiers) and mixtures of         polyalkylenes and starch.         5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).         6. Copolymers of styrene or α-methylstyrene with dienes or         acrylic derivatives, for example styrene/butadiene,         styrene/acrylonitrile, styrene/alkyl methacrylate,         styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl         methacrylate, styrene/maleic anhydride,         styrene/acrylonitrile/methyl acrylate; mixtures of high impact         strength of styrene copolymers and another polymer, for example         a polyacrylate, a diene polymer or an ethylene/propylene/diene         terpolymer; and block copolymers of styrene such as         styrene/butadiene/styrene, styrene/isoprene/styrene,         styrene/ethylene/butylene/styrene or         styrene/ethylene/propylene/styrene.         7. Graft copolymers of styrene or α-methylstyrene, for example         styrene on polybutadiene, styrene on polybutadiene-styrene or         polybutadiene-acrylonitrile copolymers; styrene and         acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,         acrylonitrile and methyl methacrylate on polybutadiene; styrene         and maleic anhydride on polybutadiene; styrene, acrylonitrile         and maleic anhydride or maleimide on polybutadiene; styrene and         maleimide on polybutadiene; styrene and alkyl acrylates or         methacrylates on polybutadiene; styrene and acrylonitrile on         ethylene/propylene/diene terpolymers; styrene and acrylonitrile         on polyalkyl acrylates or polyalkyl methacrylates, styrene and         acrylonitrile on acrylate/butadiene copolymers, as well as         mixtures thereof with the copolymers listed under 6), for         example the copolymer mixtures known as ABS, MBS, ASA or AES         polymers.         8. Halogen-containing polymers such as polychloroprene,         chlorinated rubbers, chlorinated and brominated copolymer of         isobutylene-isoprene (halobutyl rubber), chlorinated or         sulfochlorinated polyethylene, copolymers of ethylene and         chlorinated ethylene, epichlorohydrin homo- and copolymers,         especially polymers of halogen-containing vinyl compounds, for         example polyvinyl chloride, polyvinylidene chloride, polyvinyl         fluoride, polyvinylidene fluoride, as well as copolymers thereof         such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl         acetate or vinylidene chloride/vinyl acetate copolymers.         9. Polymers derived from α,β-unsaturated acids and derivatives         thereof such as polyacrylates and polymethacrylates; polymethyl         methacrylates, polyacrylamides and polyacrylonitriles,         impact-modified with butyl acrylate.         10. Copolymers of the monomers mentioned under 9) with each         other or with other unsaturated monomers, for example         acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate         copolymers, acrylonitrile/alkoxyalkyl acrylate or         acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl         methacrylate/butadiene terpolymers.         11. Polymers derived from unsaturated alcohols and amines or the         acyl derivatives or acetals thereof, for example polyvinyl         alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl         benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl         phthalate or polyallyl melamine; as well as their copolymers         with olefins mentioned in 1) above.         12. Homopolymers and copolymers of cyclic ethers such as         polyalkylene glycols, polyethyllene oxide, polypropylene oxide         or copolymers thereof with bisglycidyl ethers.         13. Polyacetals such as polyoxymethylene and those         polyoxymethylenes which contain ethylene oxide as a comonomer;         polyacetals modified with thermoplastic polyurethanes, acrylates         or MBS.         14. Polyphenylene oxides and sulfides, and mixtures of         polyphenylene oxides with styrene polymers or polyamides.         15. Polyurethanes derived from hydroxyl-terminated polyethers,         polyesters or polybutadienes on the one hand and aliphatic or         aromatic polyisocyanates on the other, as well as precursors         thereof.         16. Polyamides and copolyamides derived from diamines and         dicarboxylic acids and/or from aminocarboxylic acids or the         corresponding lactams, for example polyamide 4, polyamide 6,         polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11,         polyamide 12, aromatic polyamides starting from m-xylene diamine         and adipic acid; polyamides prepared from hexamethylenediamine         and isophthalic or/and terephthalic acid and with or without an         elastomer as modifier, for example         poly-2,4,4,-trimethylhexamethylene terephthalamide or         poly-m-phenylene isophthalamide; and also block copolymers of         the aforementioned polyamides with polyolefins, olefin         copolymers, ionomers or chemically bonded or grafted elastomers;         or with polyethers, e.g. with polyethylene glycol, polypropylene         glycol or polytetramethylene glycol; as well as polyamides or         copolyamides modified with EPDM or ABS; and polyamides condensed         during processing (RIM polyamide systems).         17. Polyureas, polyimides, polyamide-imides, polyetherimids,         polyesterimids, polyhydantoins and polybenzimidazoles.         18. Polyesters derived from dicarboxylic acids and diols and/or         from hydroxycarboxylic acids or the corresponding lactones, for         example polyethylene terephthalate, polybutylene terephthalate,         poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene         naphthalate (PAN) and polyhydroxybenzoates, as well as block         copolyether esters derived from hydroxyl-terminated polyethers;         and also polyesters modified with polycarbonates or MBS.         19. Polycarbonates and polyester carbonates.         20. Polysulfones, polyether sulfones and polyether ketones.         21. Crosslinked polymers derived from aldehydes on the one hand         and phenols, ureas and melamines on the other hand, such as         phenol/formaldehyde resins, urea/formaldehyde resins and         melamine/formaldehyde resins.         22. Drying and non-drying alkyd resins.         23. Unsaturated polyester resins derived from copolyesters of         saturated and unsaturated dicarboxylic acids with polyhydric         alcohols and vinyl compounds as crosslinking agents, and also         halogen-containing modifications thereof of low flammability.         24. Crosslinkable acrylic resins derived from substituted         acrylates, for example epoxy acrylates, urethane acrylates or         polyester acrylates.         25. Alkyd resins, polyester resins and acrylate resins         crosslinked with melamine resins, urea resins, isocyanates,         isocyanurates, polyisocyanates or epoxy resins.         26. Crosslinked epoxy resins derived from aliphatic,         cycloaliphatic, heterocyclic or aromatic glycidyl compounds,         e.g. products of diglycidyl ethers of bisphenol A and bisphenol         F, which are crosslinked with customary hardeners such as         anhydrides or amines, with or without accelerators.         27. Natural polymers such as cellulose, rubber, gelatin and         chemically modified homologous derivatives thereof, for example         cellulose acetates, cellulose propionates and cellulose         butyrates, or the cellulose ethers such as methyl cellulose; as         well as rosins and their derivatives.         28. Blends of the aforementioned polymers (polyblends), for         example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS,         PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE,         PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,         POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers,         PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.         29. Naturally occurring and synthetic organic materials which         are pure monomeric compounds or mixtures of such compounds, for         example mineral oils, animal and vegetable fats, oil and waxes,         or oils, fats and waxes based on synthetic esters (e.g.         phthalates, adipates, phosphates or trimellitates) and also         mixtures of synthetic esters with mineral oils in any weight         ratios, typically those used as spinning compositions, as well         as aqueous emulsions of such materials.         30. Aqueous emulsions of natural or synthetic rubber, e.g.         natural latex or latices of carboxylated styrene/butadiene         copolymers.

This invention therefore additionally relates to a composition comprising an organic material subject to degradation induced by light, heat or oxidation and the stabilizer mixture described above.

The compositions according to the present invention preferably do not contain a mineral oil.

Further, the organic material is preferably different from polyethylene, when component (I) is the combination of the compounds (B-1-a-1) and (B-7-a), in particular the combination of a compound of the class (β-1) and a compound of the class (β-7); and, at the same time, component (II) is Zn carboxylate, in particular an organic salt of Zn.

A preferred embodiment of the present invention relates to polypropylene containing a compound of the formula (B-1), a compound of the formula (B-7) and a Zn-carboxylate;

in which R₁, R₃, R₄ and R₅ independently of one another are hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, phenyl which is substituted by —OH and/or C₁-C₁₀alkyl; C₇-C₉phenylalkyl, C₇-C₉-phenylalkyl which is substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I)

R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene or C₁-C₄alkylenedi(B₅—C₇cycloalkylene), or the radicals R₁, R₂ and R₃, together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or R₄ and R₅, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring,

R₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl, and

b₁ is a number from 2 to 50, with the proviso that at least one of the radicals R₁, R₃, R₄ and R₅ is a group of the formula (b-I);

wherein A₁ is hydrogen or C₁-C₄alkyl, A₂ is a direct bond or C₁-C₁₀alkylene, and n₁ is a number from 2 to 50.

Another embodiment of the present invention is a method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material the stabilizer mixture described above.

The organic material is preferably a synthetic polymer, in particular from one of the above groups. Polyolefins are preferred and polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer are particularly preferred.

The components (I), (II) and optionally (X-1) and/or (X-2), as well as optionally component (XX) may be added to the organic material to be stabilized either individually or mixed with one another.

The total amount of the two different sterically hindered amine compounds (component (I)) in the organic material to be stabilized is preferably 0.005 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relative to the weight of the organic material.

The Mg and/or Zn compounds (component (II)) are present in the organic material in a total amount of preferably 0.005 to 1%, in particular 0.05 to 0.2%, relative to the weight of the organic material.

The pigment (component (X-1)) is optionally present in the organic material in an amount of preferably 0.01 to 10%, in particular 0.05 to 1%, relative to the weight of the organic material.

The UV absorber (component (X-2)) is optionally present in the organic material in an amount of preferably 0.01 to 1%, in particular 0.05 to 0.5%, relative to the weight of the organic material.

The total amount of component (X-3) (the pigment in combination with the UV absorber) is preferably 0.01 to 10%, relative to the weight of the organic material. The weight ratio of the UV absorber to the pigment is for example 2:1 to 1:10.

When the pigment used is titanium dioxide in combination with an organic pigment as described above, titanium dioxide is preferably present in the organic material in an amount of 0.01 to 5%, relative to the weight of the organic material, and the organic pigment may be present in an amount of, for example, 0.01 to 2%, relative to the weight of the organic material.

The Ca compound (component (XX)) is optionally present in the organic material in an amount of e.g. 0.005 to 1%, preferably 0.05 to 0.2%.

The weight ratio of the two different sterically hindered amine compounds forming component (I) is for example 1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I):(II) is for example 1:10 to 20:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I):(X-1) is for example 1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I):(X-2) is for example 1:5 to 5:1, preferably 1:2 to 2:1.

The weight ratio of the components (I):(X-3) is for example 1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The weight ratio of the components (I):(XX) is for example 1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.

The above components can be incorporated into the organic material to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the organic material, if necessary with subsequent evaporation of the solvent. The components can be added to the organic material in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight.

If desired, the components (I), (II) and optionally (X-1) and/or (X-2), as well as component (XX) can be melt blended with each other before incorporation in the organic material. They can be added to a polymer before or during the polymerization or before the crosslinking.

The materials stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or putties.

Examples of Processing or Transformation of the Plastics According to the Present Invention are:

Injection blow molding, extrusion, blow molding, rotomolding, in mold decoration (back injection), slush molding, injection molding, co-injection molding, forming, compression molding, pressing, film extrusion (cast film; blown film), fiber spinning (woven, non-woven), drawing (uniaxial, biaxial), annealing, deep drawing, calandering, mechanical transformation, sintering, coextrusion, coating, lamination, crosslinking (radiation, peroxide, silane), vapor deposition, weld together, glue, vulkanization, thermoforming, pipe extrusion, profile extrusion, sheet extrusion; sheet casting, spin coating, strapping, foaming, recycling/rework, extrusion coating, visbreaking (peroxide, thermal), fiber melt blown, spun bonded, surface treatment (corona discharge, flame, plasma), sterilization (by gamma rays, electron beams), cast polymerization (R&M process, RAM extrusion), gel-coating, tape extrusion, GMT-process, SMC-process, plastisol, and dipping (PVC, latex).

The Plastics According to the Present Invention May be Used for the Preparation of:

I-1) Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements.

I-2) Automotive applications, in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter/filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners/fixings, front end module, glass, hinges, lock systems, luggage/roof racks, pressed/stamped parts, seals, side impact protection, sound deadener/insulator and sunroof.

I-3) Road traffic devices, in particular sign postings, posts for road marking, car accessories, warning triangles, medical cases, helmets, tires.

I-4) Devices for plane, railway, motor car (car, motorbike) including furnishings.

I-5) Devices for space applications, in particular rockets and satellites, e.g. reentry shields.

I-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.

II-1) Appliances, cases and coverings in general and electric/electronic devices (personal computer, telephone, handy, printer, television-sets, audio and video devices), flower pots, satellite TV bowl, and panel devices.

II-2) Jacketing for other materials such as steel or textiles.

II-3) Devices for the electronic industry, in particular insulation for plugs, especially computer plugs, cases for electric and electronic parts, printed boards, and materials for electronic data storage such as chips, check cards or credit cards.

II-4) Electric appliances, in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.

II-5) Covers for lights (e.g. street-lights, lamp-shades).

II-6) Applications in wire and cable (semi-conductor, insulation and cable-jacketing).

II-7) Foils for condensers, refrigerators, heating devices, air conditioners, encapsulating of electronics, semi-conductors, coffee machines, and vacuum cleaners.

III-1) Technical articles such as cogwheel (gear), slide fittings, spacers, screws, bolts, handles, and knobs.

III-2) Rotor blades, ventilators and windmill vanes, solar devices, swimming pools, swimming pool covers, pool liners, pond liners, closets, wardrobes, dividing walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves, and conveyor belts.

III-3) Sanitary articles, in particular shower cubicles, lavatory seats, covers, and sinks.

III-4) Hygienic articles, in particular diapers (babies, adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, tubs, mobile toilets, tooth brushes, and bed pans.

III-5) Pipes (cross-linked or not) for water, waste water and chemicals, pipes for wire and cable protection, pipes for gas, oil and sewage, guttering, down pipes, and drainage systems.

III-6) Profiles of any geometry (window panes) and siding.

III-7) Glass substitutes, in particular extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.

III-8) Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.

III-9) Intake and outlet manifolds.

III-10) Cement-, concrete-, composite-applications and covers, siding and cladding, hand rails, banisters, kitchen work tops, roofing, roofing sheets, tiles, and tarpaulins.

IV-1) Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.

IV-2) Woven fabrics continuous and staple, fibers (carpets/hygienic articles/geotextiles/monofilaments; filters; wipes/curtains (shades)/medical applications), bulk fibers (applications such as gown/protection clothes), nets, ropes, cables, strings, cords, threads, safety seat-belts, clothes, underwear, gloves; boots; rubber boots, intimate apparel, garments, swimwear, sportswear, umbrellas (parasol, sunshade), parachutes, paraglides, sails, “balloon-silk”, camping articles, tents, airbeds, sun beds, bulk bags, and bags.

IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps, ponds, dumps, walls roofing membranes, geomembranes, swimming pools, curtains (shades)/sun-shields, awnings, canopies, wallpaper, food packing and wrapping (flexible and solid), medical packaging (flexible & solid), airbags/safety belts, arm- and head rests, carpets, centre console, dashboard, cockpits, door, overhead console module, door trim, headliners, interior lighting, interior mirrors, parcel shelf, rear luggage cover, seats, steering column, steering wheel, textiles, and trunk trim.

V) Films (packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.

VI-1) Food packing and wrapping (flexible and solid), BOPP, BOPET, bottles.

VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans.

VI-3) Cartridges, syringes, medical applications, containers for any transportation, waste baskets and waste bins, waste bags, bins, dust bins, bin liners, wheely bins, container in general, tanks for water/used water/chemistry/gas/oil/gasoline/diesel; tank liners, boxes, crates, battery cases, troughs, medical devices such as piston, ophthalmic applications, diagnostic devices, and packing for pharmaceuticals blister.

VII-1) Extrusion coating (photo paper, tetrapack, pipe coating), household articles of any kind (e.g. appliances, thermos bottle/clothes hanger), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap-closures.

VII-2) Support devices, articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.

VII-3) Furniture in general, foamed articles (cushions, impact absorbers), foams, sponges, dish clothes, mats, garden chairs, stadium seats, tables, couches, toys, building kits (boards/figures/balls), playhouses, slides, and play vehicles.

VII-4) Materials for optical and magnetic data storage.

VII-5) Kitchen ware (eating, drinking, cooking, storing).

VII-6) Boxes for CD's, cassettes and video tapes; DVD electronic articles, office supplies of any kind (ball-point pens, stamps and ink-pads, mouse, shelves, tracks), bottles of any volume and content (drinks, detergents, cosmetics including perfumes), and adhesive tapes.

VII-7) Footwear (shoes/shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technologies.

VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO₂, mica, nanocomposites, dolomite, silicates, glass, asbestos).

The stabilized material may additionally also contain various conventional additives, for example:

1. Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butyl-phenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methyl-phenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyl-heptadec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis-(3,6-di-sec-amylphenol), 4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example 2, 2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexyl-phenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di-tert-butylphenol), 4,4′-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example 3, 5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1, 3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, Bis[4-(1′,3′-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-und dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono-und dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono-und dialkylated tert-octyl-phenothiazines, N-allylphenothiazin, N,N,N′,N′-tetraphenyl-1,4-diamino-but-2-ene, N,N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

Nickel compounds, for example nickel complexes of 2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

3. Metal Deactivators, for example N,N′-diphenyloxamide, N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl) hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)-oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and Phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide Scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

9. Basic Co-Stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.

10. Nucleating Agents, for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (“ionomers”).

11. Fillers and Reinforcing Agents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

12. Other Additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

13. Benzofuranones and Indolinones, for example those disclosed in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312, U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The weight ratio of the total amount of components (I), (II) and optionally (X-1) and/or (X-2), as well as optionally component (XX) to the total amount of the conventional additives can be, for example, 100:1 to 1:100.

The examples below illustrate the invention in greater detail. All percentages and parts are by weight, unless stated otherwise.

Stabilizers Used in the Following Examples I to IV:

(For the polymeric compounds, the mean degree of polymerization is indicated in each case.)

Compound (B-1-a-1):

with b₁ being 4.5. Compound (B-2-a-1):

where R′ is

Compound (B-7-a-1):

with n₁ being 5.1.

Compound (X-2-a):

Example I Light Stabilization of Polypropylene Tapes

100 parts of polypropylene powder (melt flow index: 3.2 g/10 min at 230° C. and 2160 g) are blended in a barrel mixer with 0.05 parts of pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.05 parts of tris[2,4-di-tert-butylphenyl]phosphite and the stabilizer system indicated in Table 1. Then, the blend is compounded in an extruder at temperatures of 180°-220° C. The granules obtained on extrusion and granulation are transformed into films at 220″-260° C. in a second extruder equipped with a flat sheet die. The films are cut into ribbons which are drawn to achieve a stretch ratio of 1:6. The tapes obtained with this procedure are finally 50 μm thick and 2.5 mm wide.

The tapes are mounted without tension on sample holders and exposed to natural weathering in Florida (450 South, direct, approximately 145 kLy/year). Periodically, the tensile strength of the exposed tapes is measured. The received energy (in kLy) corresponding to a loss of 50% (E₅₀) of the initial tensile strength or the % retained tensile strength after 320 kLy is a measure for the stabilizing efficiency of the stabilizer system. The values obtained are summarized in Table 1.

TABLE 1 E₅₀ (kLy) to 50% retained tensile strength or % retained tensile Stabilizer System strength after 320 kLy 0.1% of Mg stearate 58    0.05% of (B-1-a-1) + 0.05% of (B-7-a-1) + 78% 0.1% of Mg stearate

Example II Light Stabilization of Polypropylene Homopolymer Films

100 parts of unstabilized polypropylene powder (melt flow index: 3.8 g/10 min at 230° C. and 2160 g) are homogenized at 200° C. for 10 min in a Brabender plastograph with 0.05 parts of pentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.10 parts of tris{2,4-di-tert-butylphenyl}phosphite and the stabilizer system indicated in Tables 2a, 2b, 2c and 2d. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 min at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C., without water-spraying).

Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer. The exposure time corresponding to formation of a carbonyl absorbance of 0.1 in hours (T_(0.1)) is a measure for the efficiency of the stabilizer system. The values obtained are summarized in Tables 2a, 2b, 2c and 2d.

TABLE 2a T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.1% of Mg stearate + 0.1% of (X-2-a) 360 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 1960 0.1% of Mg stearate + 0.1% of (X-2-a) 0.025% of (B-2-a-1) + 0.025% of (B-7-a-1) + 1820 0.1% of Mg stearate + 0.1% of (X-2-a)

TABLE 2b T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.1% of Zn stearate + 0.5% of TiO₂ (rutile) 430 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 1540 0.1% of Zn stearate + 0.5% of TiO₂ (rutile) 0.025% of (B-2-a-1) + 0.025% of (B-7-a-1) + 1840 0.1% of Zn stearate + 0.5% of TiO₂ (rutile)

TABLE 2c T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 2020 0.1% of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO₂ (rutile)

TABLE 2d T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 2320 0.1% of hydrotalcite (DHT-4A (RTM)) + 0.1% of (X-2-a)

Example III Light Stabilization of Polypropylene Copolymer Films

100 parts of unstabilized copolypropylene powder (melt flow index: 6 g/10 min at 230° C. and 2160 g; 10% ethylene monomer) are homogenized at 200° C. for 10 min in a Brabender plastograph with 0.05 parts of pentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, 0.10 parts of tris{2,4-di-tert-butylphenyl}phosphite and the stabilizer system indicated in Table 3. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 min at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C., without water-spraying).

Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer. The exposure time corresponding to formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the stabilizer system. The values obtained are summarized in Table 3.

TABLE 3 T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.1% of hydrotalcite (DHT-4A (RTM)) + 390 0.5% of TiO₂ (rutile) 0.05% of (B-1-a-1) + 0.05% of (B-7-a-1) + 4000 0.1% of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO₂ (rutile) 0.05% of (B-2-a-1) + 0.05% of (B-7-a-1) + 4960 0.1% of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO₂ (rutile)

Example IV Light Stabilization of Polyethylene Hd Films

100 parts of unstabilized high density polyethylene powder (density: 0.964 g cm⁻³, melt flow index: 5.0 g/10 min at 190° C. and 2160 g) are homogenized at 180° C. for 10 min in a Brabender plastograph with 0.03 parts of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate and the stabilizer system indicated in Tables 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4h and 4i. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 min at 210° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm×25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63±2° C., without water-spraying).

Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer. The exposure time corresponding to formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the stabilizer mixture. The values obtained are summarized in Table 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4h and 4i.

TABLE 4a T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 18060 0.1% of Mg stearate

TABLE 4b T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 18055 0.1% of hydrotalcite (DHT-4A (RTM))

TABLE 4c T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 22210 0.05% of Mg stearate + 0.05% of Ca stearate

TABLE 4d T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 15680 0.05% of hydrotalcite (DHT-4A (RTM)) + 0.1% of Ca stearate

TABLE 4e T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 23040 0.05% of hydrotalcite (DHT-4A (RTM)) + 0.1% of Mg stearate

TABLE 4f T_(0.1) in hours to Stabilizer system 0.1 carbonyl absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + >28700 0.1% of Mg stearate + 0.5% of TiO₂ (rutile)

TABLE 4g T_(0.1) in hours to 0.1 carbonyl Stabilizer system absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + >28700 0.05% of Mg stearate + 0.5% of TiO₂ (rutile) + 0.05% of Ca stearate

TABLE 4h T_(0.1) in hours to 0.1 carbonyl Stabilizer system absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + >28700 0.05% of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO₂ (rutile) + 0.05% of Ca stearate

TABLE 4i T_(0.1) in hours to 0.1 carbonyl Stabilizer system absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + >28700 0.05% of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO₂ (rutile) + 0.05% of Mg stearate 

1. A stabilizer mixture containing (I) two different sterically hindered amine compounds, and (II) at least one compound selected from the group consisting of an organic salt of Zn, an inorganic salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, Mg oxide and Mg hydroxide; with the proviso that component (I) is different from the combination of the compounds (B-8-a) and (B-8-b)

wherein n₂ and n₂* are a number from 2 to 50; and with the proviso that, when component (I) is the combination of the compounds (B-1-a-1) and (B-7-a);

wherein b₁ is a number from 2 to 50,

wherein n₁ is a number from 2 to 50; and, at the same time, component (II) is a Zn carboxylate; the stabilizer mixture additionally contains as a further component (X-1) a pigment or (X-2) an UV absorber or (X-3) a pigment and an UV absorber.
 2. A stabilizer mixture according to claim 1 wherein the two different sterically hindered amine compounds of component (I) are selected from the group consisting of (α-1) a compound of the formula (A-1)

in which E₁ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl, m₁ is 1, 2 or 4, if m₁ is 1, E₂ is C₁-C₂₅alkyl, if m₁ is 2, E₂ is C₁-C₁₄alkylene or a group of the formula (a-I)

wherein E₃ is C₁-C₁₀alkyl or C₂-C₁₀alkenyl, E₄ is C₁-C₁₀alkylene, and E₅ and E₆ independently of one another are C₁-C₄alkyl, cyclohexyl or methylcyclohexyl, and if m₁ is 4, E₂ is C₄-C₁₀alkanetetrayl; (α-2) a compound of the formula (A-2)

in which two of the radicals E₇ are —COO—(C₁-C₂₀alkyl), and two of the radicals E₇ are a group of the formula (a-II)

with E₈ having one of the meanings of E₁; (α-3) a compound of the formula (A-3)

in which E₉ and E₁₀ together form C₂-C₁₄alkylene, E₁₁ is hydrogen or a group -Z₁-COO-Z₂, Z₁ is C₂-C₁₄alkylene, and Z₂ is C₁-C₂₄alkyl, and E₁₂ has one of the meanings of E₁; (α-4) a compound of the formula (A-4)

wherein the radicals E₁₃ independently of one another have one of the meanings of E₁, the radicals E₁₄ independently of one another are hydrogen or C₁-C₁₂alkyl, and E₁₅ is C₁-C₁₀alkylene or C₃-C₁₀alkylidene; (α-5) a compound of the formula (A-5)

wherein the radicals E₁₆ independently of one another have one of the meanings of E₁; (α-6) a compound of the formula (A-6)

in which E₁₇ is C₁-C₂₄alkyl, and E₁₈ has one of the meanings of E₁; (α-7) a compound of the formula (A-7)

in which E₁₉, E₂₀ and E₂₁ independently of one another are a group of the formula (a-III)

wherein E₂₂ has one of the meanings of E₁; (α-8) a compound of the formula (A-8)

wherein the radicals E₂₃ independently of one another have one of the meanings of E₁, and E₂₄ is hydrogen, C₁-C₁₂alkyl or C₁-C₁₂alkoxy; (α-9) a compound of the formula (A-9)

wherein m₂ is 1, 2 or 3, E₂₅ has one of the meanings of E₁, and when m₂ is 1, E₂₆ is a group

when m₂ is 2, E₂₆ is C₂-C₂₂alkylene, and when m₂ is 3, E₂₆ is a group of the formula (a-IV)

wherein the radicals E₂₇ independently of one another are C₂-C₁₂alkylene, and the radicals E₂₈ independently of one another are C₁-C₁₂alkyl or C₅-C₁₂cycloalkyl; (α-10) a compound of the formula (A-10)

wherein the radicals E₂₉ independently of one another have one of the meanings of E₁, and E₃₀ is C₂-C₂₂alkylene, C₅-C₇cycloalkylene, C₁-C₄alkylenedi(C₅-C₇cycloalkylene), phenylene or phenylenedi(C₁-C₄alkylene); (β-1) a compound of the formula (B-1)

in which R₁, R₃, R₄ and R₅ independently of one another are hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, phenyl which is substituted by —OH and/or C₁-C₁₀alkyl; C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I)

R₂ is C₂-C₁₈alkylene, C₅-C₇cycloalkylene or C₁-C₄alkylenedi(B₅—C₇cycloalkylene), or the radicals R₁, R₂ and R₃, together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or R₄ and R₅, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, R₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl, and b₁ is a number from 2 to 50, with the proviso that at least one of the radicals R₁, R₃, R₄ and R₅ is a group of the formula (b-I); (β-2) a compound of the formula (B-2)

wherein R₇ and R₁₁ independently of one another are hydrogen or C₁-C₁₂alkyl, R₈, R₉ and R₁₀ independently of one another are C₂-C₁₀alkylene, and X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are a group of (b-II),

in which R₁₂ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, —OH— and/or C₁-C₁₀alkyl-substituted phenyl, C₇-C₉phenylalkyl, C₇-C₉phenylalkyl which is substituted on the phenyl radical by —OH and/or C₁-C₁₀alkyl; or a group of the formula (b-I) as defined above, and R₁₃ has one of the meanings of R(β-3) a compound of the formula (B-3)

in which R₁₄ is C₁-C₁₀alkyl, C₅-C₁₂cycloalkyl, C₁-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl or C₁-C₁₀alkyl-substituted phenyl, R₁₅ is C₃-C₁₀alkylene, R₁₆ has one of the meanings of R₆, and b₂ is a number from 2 to 50; (β-4) a compound of the formula (B-4)

in which R₁₇ and R₂₁ independently of one another are a direct bond or a —N(X₉)—CO—X₁₀—CO—N(X₁₁)— group, where X₉ and X₁₁ independently of one another are hydrogen, C₁-C₈alkyl, C₅-C₁₂cycloalkyl, phenyl, C₇-C₉phenylalkyl or a group of the formula (b-I), X₁₀ is a direct bond or C₁-C₄alkylene, R₁₈ has one of the meanings of R₆, R₁₉, R₂₀, R₂₃ and R₂₄ independently of one another are hydrogen, C₁-C₃₀alkyl, C₅-C₁₂cycloalkyl or phenyl, R₂₂ is hydrogen, C₁-C₃₀alkyl, C₅-C₁₂cycloalkyl, phenyl, C₇-C₉phenylalkyl or a group of the formula (b-I), and b₃ is a number from 1 to 50; (β-5) a compound of the formula (B-5)

in which R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ independently of one another are a direct bond or C₁-C₁₀alkylene, R₃₀ has one of the meanings of R₆, and b₄ is a number from 1 to 50; (β-6) a product (B-6) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1) with cyanuric chloride, with a compound of the formula (B-6-2)

in which b′₅, b″₅ and b′″₅ independently of one another are a number from 2 to 12, R₃₁ is hydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl, and R₃₂ has one of the meanings of R₆; (β-7) a compound of the formula (B-7)

wherein A₁ is hydrogen or C₁-C₄alkyl, A₂ is a direct bond or C₁-C₁₀alkylene, and n₁ is a number from 2 to 50; (β-8) at least one compound of the formulae (B-8-a) and (B-8-b)

wherein n₂ and n₂* are a number from 2 to 50; (β-9) a compound of the formula (B-9)

wherein A₃ and A₄ independently of one another are hydrogen or C₁-C₈alkyl, or A₃ and A₄ together form a C₂-C₁₄alkylene group, and the variables n₃ independently of one another are a number from 1 to 50; and (β-10) a compound of the formula (B-10)

wherein n₄ is a number from 2 to 50, A₅ is hydrogen or C₁-C₄alkyl, the radicals A₆ and A₇ independently of one another are C₁-C₄alkyl or a group of the formula (b-I), with the proviso that at least 50% of the radicals A₇ are a group of the formula (b-I) and with the proviso that the stablizer mixtures containing both of the two different sterically hindered amine compounds selected from the group consisting of the classes (β-1), (β-2), (β-6), (β-7) and (β-8) are excluded.
 3. A stabilizer mixture according to claim 2, wherein the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the classes (α-1), (α-2), (α-3), (α-4), (α-5), (α-6), (α-7), (α-8), (α-9) and (α-10).
 4. A stabilizer mixture according to claim 2, wherein the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the classes (β-3), (β-4), (β-5), (β-9) and (β-10).
 5. A stabilizer mixture according to claim 2, wherein one of the two different sterically hindered amine compounds of component (I) is selected from the group consisting of the classes (α-1), (α-2), (α-3), (α-4), (α-5), (α-6), (α-7), (α-8), (α-9) and (α-10), and the other of the two different sterically hindered amine compounds of component (I) is selected from the group consisting of the classes (β-1), (β-2), (β-3), (β-4), (β-5), (β-6), (β-7), (β-8), (β-9) and (β-10).
 6. A stabilizer mixture according to claim 2, wherein one of the two different sterically hindered amine compounds of component (I) is selected from the class (β-1) with the proviso that the other of the two different sterically hindered amine compounds selected from the group consisting of the classes ((β-1), (β-2), (β-6), (β-7), and (β3-8) is excluded.
 7. A stabilizer mixture according to claim 2, wherein one of the two different sterically hindered amine compounds of component (I) is selected from the class (β-1), and the other of the two different sterically hindered amine compounds of component (I) is selected from the class (α-1).
 8. A stabilizer mixture according to claim 2, wherein the two different sterically hindered amine compounds of component (I) are selected from different classes.
 9. A stabilizer mixture according to claim 2, wherein m₁ is 1, 2 or 4, if m₁ is 1, E₂ is C₁₂-C₂₀alkyl, if m₁ is 2, E₂ is C₂-C₁₀alkylene or a group of the formula (a-I) E₃ is C₁-C₄alkyl, E₄ is C₁-C₆alkylene, and E₅ and E₆ independently of one another are C₁-C₄alkyl, and if m₁ is 4, E₂ is C₄-C₈alkanetetrayl; two of the radicals E₇ are —COO—(C₁₀-C₁₅alkyl), and two of the radicals E₇ are a group of the formula (a-II); E₉ and E₁₀ together form C₉-C₁₃alkylene, E₁₁ is hydrogen or a group -Z₁-COO-Z₂, Z₁ is C₂-C₆alkylene, and Z₂ is C₁₀-C₁₆alkyl; E₁₄ is hydrogen, and E₁₅ is C₂-C₆alkylene or C₃-C₅alkylidene; E₁₇ is C₁₀-C₁₄alkyl; E₂₄ is C₁-C₄alkoxy; m₂ is 1, 2 or 3,

when m₂ is 1, E₂₆ is a group when m₂ is 2, E₂₆ is C₂-C₆alkylene, and when m₂ is 3, E₂₆ is a group of the formula (a-IV) the radicals E₂₇ independently of one another are C₂-C₆alkylene, and the radicals E₂₈ independently of one another are C₁-C₄alkyl or C₅-C₈cycloalkyl; and E₃₀ is C₂-C₈alkylene; R₁ and R₃ independently of one another are a group of the formula (b-I), R₂ is C₂-C₈alkylene, R₄ and R₅ independently of one another are hydrogen, C₁-C₁₂alkyl, C₅-C₈cycloalkyl or a group of the formula (b-I), or the radicals R₄ and R₅, together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and b₁ is a number from 2 to 25; R₇ and R₁₁ independently of one another are hydrogen or C₁-C₄alkyl, R₈, R₉ and R₁₀ independently of one another are C₂-C₄alkylene, and X₁, X₂, X₃, X₄, X₅, X₆, X₇ and X₈ independently of one another are a group of the formula (b-II), R₁₂ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl or a group of the formula (b-I); R₁₄ is C₁-C₄alkyl, R₁₅ is C₃-C₆alkylene, and b₂ is a number from 2 to 25; R₁₇ and R₂₁ independently of one another are a direct bond or a group —N(X₉)—CO—X₁₀—CO—N(X₁₁)—, X₉ and X₁₁ independently of one another are hydrogen or C₁-C₄alkyl, X₁₀ is a direct bond, R₁₉ and R₂₃ are C₁-C₂₅alkyl or phenyl, R₂₀ and R₂₄ are hydrogen or C₁-C₄alkyl, R₂₂ is C₁-C₂₅alkyl or a group of the formula (b-I), and b₃ is a number from 1 to 25; R₂₅, R₂₆, R₂₇, R₂₈ and R₂₉ independently of one another are a direct bond or C₁-C₄alkylene, and b₄ is a number from 1 to 25; b′₅, b″₅ and b′″₅ independently of one another are a number from 2 to 4, and R₃₁ is hydrogen, C₁-C₄alkyl, C₅-C₈cycloalkyl, phenyl or benzyl; A₁ is hydrogen or methyl, A₂ is a direct bond or C₂-C₆alkylene, and n₁ is a number from 2 to 25; n₂ and n₂* are a number from 2 to 25; A₃ and A₄ independently of one another are hydrogen or C₁-C₄alkyl, or A₃ and A₄ together form a C₉-C₁₃alkylene group, and the variables n₃ independently of one another are a number from 1 to 25; n₄ is a number from 2 to 25, A₅ and A₉ independently of one another are C₁-C₄alkyl, and A₇ is C₁-C₄alkyl or a group of the formula (b-I) with the proviso that at least 50% of the radicals A₇ are a group of the formula (b-I).
 10. A stabilizer mixture according to claim 1, wherein the two different sterically hindered amine compounds of component (I) are selected from the group consisting of the compounds of the formulae (A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a), (A-3-b), (A-4-a), (A-4-b), (A-5), (A-6-a), (A-7), (A-8-a), (A-9-a), (A-9-b), (A-9-c), (A-10-a), (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-4-a), (B-4-b) and (B-4-c), a product (B-6-a) and the compounds of the formulae (B-7-a), (B-8-a), (B-8-b), (B-9-a) and (B-10-a);

wherein E₁ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉-phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl;

in which two of the radicals E₇ are —COO—C₁₃H₂₇ and two of the radicals E₇ are

and E₈ has one of the meanings of E₁;

wherein E₁₂ has one of the meanings of E₁;

wherein E₁₃ has one of the meanings of E₁;

wherein E₁₆ has one of the meanings of E₁,

wherein E₁₈ has one of the meanings of E₁;

in which E₁₉, E₂₀ and E₂₁ independently of one another are a group of the formula (a-III)

wherein E₂₂ has one of the meanings of E₁;

wherein E₂₃ has one of the meanings of E₁;

wherein E₂₅ has one of the meanings of E₁;

wherein E₂₉ has one of the meanings of E₁,

wherein b₁ is a number from 2 to 20 and R₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl;

wherein R₁₃ has one of the meanings of R₆,

wherein b₂ is a number from 2 to 20 and R₁₆ has one of the meanings of R₆;

wherein b₃ is a number from 1 to 20 and R₁₈ has one of the meanings of R₆;

wherein b₄ is a number from 1 to 20 and R₃₀ has one of the meanings of R₆; a product (B-6-a) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-6-1-a) with cyanuric chloride, with a compound of the formula (B-6-2-a)

in which R₃₂ has one of the meanings of R₆;

wherein n₁ is a number from 2 to 20;

wherein n₂ and n₂* are a number from 2 to 20;

wherein the variables n₃ independently of one another are a number from 1 to 20;

wherein n₄ is a number from 2 to 20, and at least 50% of the radicals A₇ are a group of the formula (b-I)

wherein R₆ is hydrogen, C₁-C₈alkyl, O., —OH, —CH₂CN, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₆alkenyl, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C₁-C₄alkyl; or C₁-C₈acyl, and the remaining radicals A₇ are ethyl.
 11. A stabilizer mixture according to claim 10 wherein the two different sterically hindered amine compounds of component (I) are a compound of the formula (A-1-b) wherein E₁ is hydrogen, and a compound of the formula (B-1-a) wherein R₆ is hydrogen.
 12. A stabilizer mixture according to claim 2 wherein E₁, E₈, E₁₂, E₁₃, E₁₆, E₁₈, E₂₂, E₂₃, E₂₅, E₂₉, R₆, R₁₃, R₁₆, R₁₈, R₃₀ and R₃₂ are hydrogen, C₁-C₄alkyl, C₁-C₁₀alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
 13. A stabilizer mixture according to claim 10 wherein E₁, E₈, E₁₂, E₁₃, E₁₆, E₈, E₂₂, E₂₃, E₂₅, E₂₉, R₆, R₁₃, R₁₆, R₁₈, R₃₀ and R₃₂ are hydrogen or methyl and E₁ and R₆ additionally are C₁-C₈alkoxy.
 14. A stabilizer mixture according to claim 1, wherein the compound of component (II) is selected from the group consisting of Mg carboxylates, Zn carboxylates, Mg oxides, Zn oxides, Mg hydroxides, Zn hydroxides, Mg carbonates and Zn carbonates.
 15. A stabilizer mixture according to claim 1, which additionally contains as a further component (X-1) a pigment or (X-2) an UV absorber or (X-3) a pigment and an UV absorber.
 16. A stabilizer mixture according to claim 1, which additionally contains as a further component (XX) an organic salt of Ca, an inorganic salt of Ca, Ca oxide or Ca hydroxide.
 17. A composition comprising an organic material subject to degradation induced by light, heat or oxidation and a stabilizer mixture according to claim
 1. 18. A composition according to claim 17 wherein the organic material is a synthetic polymer.
 19. A composition according to claim 17 wherein the organic material is a polyolefin.
 20. A composition according to claim 17 wherein the organic material is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.
 21. A method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material a stabilizer mixture according to claim
 1. 